JP3039757B2 - Low glass transition temperature copolyester carbonate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to thermoplastic resin compositions and, more particularly, to improved blow moldable copolyestercarbonate resins and articles molded therefrom.

[0002]

BACKGROUND OF THE INVENTION Aromatic copolyestercarbonate resins are a well-known class of synthetic polymeric resins generally prepared by the reaction of a polyhydric phenol with a carbonate precursor in the presence of an ester precursor, for example, US Pat. See U.S. Pat. No. 3,169,121. It has been found that these resins can be molded utilizing thermoplasticity over a wide range of molding conditions, but only the selected copolyestercarbonate resin composition is useful for blow molding. This is due to the unique requirements of the thermoplastic resin for the blow molding process operation, for example, US Pat.
See the requirements for branched copolyestercarbonate resins described in US Pat. No. 83 and 4,621,132. The branched copolyester carbonate resin is
The melt rheological behavior differs from most molding thermoplastic polymers. Most thermoplastic polymers exhibit non-Newtonian flow properties over essentially all melt processing conditions. However, in contrast to the majority of thermoplastic polymers,
Certain branched copolyester carbonates made from dihydric phenols exhibit Newtonian flow at normal processing temperatures and shear rates of less than 300 sec- ¹ .

[0003] Newtonian flow is defined as a type of flow that occurs in a liquid system where the shear rate is directly proportional to the shear force. Two other properties of the molten thermoplastic polymer are believed to be important for the molding operation: melt elasticity and melt strength. Melt elasticity is the recovery of elastic energy stored in the melt from the deformation or orientation of molecules due to shear stress. Melt strength, which may be simply defined as the toughness of the molten strand, indicates the ability of the melt to withstand stress. Both of these properties
This is important in extrusion blow molding, particularly in the production of relatively large articles by extrusion blow molding. Non-Newtonian flow properties tend to impart melt elasticity and melt strength to the polymer, thus enabling its use in blow molding.

[0004] In a conventional blow molding operation, a tube of copolyestercarbonate resin softened by heat will be vertically extruded into a mold. The extrudate is then pressed against the mold surface by a stream of compressed gas (usually air or an inert gas) to impart shape to the heat softened resin. As mentioned above, the successful molding of certain thermoplastics depends on a number of factors, including the characteristics and physical properties of the heat-softened resin.

[0005]

However, even though some branched copolyestercarbonate resins may have the properties required for satisfactory blow molding, the resulting article lacks some other desired physical properties. It is possible. For example,
The moldings may lack the desired degree of impact strength, especially at low temperatures. The present inventors have discovered that a particular class of polyester carbonate resins is represented by a branched copolyestercarbonate composition that exhibits a reduced glass transition (Tg) temperature and a reduced viscosity behavior due to shearing forces of blow molding grade resins. did. The Tg of the resin is
Decreased by the presence of aliphatic diester blocks, branching is obtained by using a specific class of trisphenol.

[0006] The non-Newtonian rheological behavior of this resin and the reduced glass transition temperature are useful for injection molding.
One example of such an application is in molded computers and business equipment housings. These large and complex parts require materials with reduced viscosity at the shear rates experienced during filling of the mold in the injection molding process. The compositions of the present invention provide the type of rheological behavior required for this application. Copolymers based on bisphenol A, alkane diacids and 1,1,1-tris- (4-hydroxyphenyl) ethane have improved processability at lower processing temperatures as well as typical non-Newtonian behavior of branched polycarbonate homopolymers. Show. The advantages are that extrusion at lower temperatures, reduced torque, smoother surface appearance of the extruded parts and the ability to co-extrude with heat sensitive materials that cannot be processed at the molding temperatures of commonly used polycarbonates. Including.

[0007] Melt-processable copolyestercarbonates having relatively high glass transition temperatures (on the order of 180 ° C. or higher) are disclosed in US Pat. No. 4,310,65.
No. 2 (DeBons et al., January 12, 1982). As used herein, the term “low glass transition temperature” or “reduced Tg” means a Tg lower than 145 ° C.

No. 4,621,132 (Qui)
nn, et al., November 4, 1986) describe a branched copolyestercarbonate resin containing a resin that is randomly branched with a trisphenol-based branching agent. These resins are made from an aromatic ester precursor (isophthaloyl dichloride).

[0009]

The present invention relates to a compound of the formula (I)

[0010]

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Wherein D is a divalent aromatic residue of a dihydric phenol used in the polymerization reaction for the production, a polymer main chain comprising repeating carbonate structural units, and a compound represented by the formula (II):

[0012]

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(Wherein n is 4 to 12, preferably 8)
A blowable thermoplastic branched copolyestercarbonate having a cyclic or repeating carboxyl chain unit of from 1 to 10, wherein the units of formulas (I) and (II) are of formula (III)

[0014]

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[0015] The copolyester carbonate comprises a copolyestercarbonate that is randomly and randomly separated by branches of the non-Newtonian flow behavior when thermally plasticized. The copolyestercarbonate resins of the present invention exhibit a reduced Tg, ie, a low glass transition temperature. The invention also includes articles blow molded from the compositions of the invention. The articles of the present invention are useful as bottles, housings for tools and equipment, structural parts for automobiles, and the like.

[0016]

DETAILED DESCRIPTION OF THE INVENTION The blow-moldable branched copolyestercarbonate resin of the present invention comprises a dihydric phenol and an ester precursor, a carbonate precursor such as phosgene, and a branching agent, 1,1,1-tris- (4-hydroxy). It may be prepared by reacting phenyl) ethane (hereinafter sometimes referred to for convenience as "THPE"). The manufacturing method may be a well-known method, for example, U.S. Pat. Nos. 3,169,121 and 4,498, which are incorporated herein by reference.
See the interfacial polymerization method described in US Pat. No. 487,896.

While the reaction conditions of the manufacturing process can vary, some of the preferred methods include dissolving or dispersing the reactants, typically a dihydric phenol and a polyfunctional organic compound, in aqueous caustic solution, the resulting mixture. To a suitable water-immiscible solvent and contacting the reactants with a carbonate precursor such as phosgene in the presence of a suitable catalyst and under controlled pH conditions. The most commonly used water-immiscible solvents include methylene chloride, 1,2-dichloroethane, chlorobenzene, toluene and the like.

The catalyst used increases the rate of polymerization of the dihydric phenol reactant with the carbonate precursor. By way of non-limiting example, representative catalysts include tertiary amines such as triethylamine, quaternary phosphonium compounds, quaternary ammonium compounds, and the like. A preferred method for producing the resin of the present invention involves a phosgenation reaction. The temperature at which the phosgenation reaction proceeds may vary from 0 ° C or lower to 100 ° C or higher. The phosgenation reaction preferably proceeds at a temperature from room temperature (25 ° C) to 50 ° C. Since the reaction is exothermic, the rate of phosgene addition may be used to control the reaction temperature. The amount of phosgene required will generally depend on the amount of compound that is a multifunctional organic reactant present.

The dihydric phenols used are known and the reactive groups are two phenolic hydroxyl groups. Some dihydric phenols have the general formula

[0020]

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Wherein A is a divalent hydrocarbon group containing 1 to about 15 carbon atoms, and a substituted divalent hydrocarbon group containing 1 to about 15 carbon atoms and a substituent such as halogen. , -S-, -S-S-, -S (= O)-, -S (=
O) _2- , -O- or -C (= O)-, and each X
Is hydrogen, halogen and an alkyl group having 1 to about 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aryl-substituted alkyl group having 7 to about 14 carbon atoms,
A monovalent hydrocarbon group such as an alkyl-substituted aryl group having 7 to about 14 carbon atoms, an alkoxy group having 1 to about 8 carbon atoms or an aryloxy group having 6 to 18 carbon atoms. Independently selected, m is 0 or 1, and a is an integer from 0 to 5.

Typical of some dihydric phenols that can be used in the practice of the present invention are (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A). Bisphenols such as 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, bis (4-hydroxyphenyl) ether, bis (3,5-
Dihydric phenol ethers such as dichloro-4-hydroxyphenyl) ether, dihydroxydiphenyls such as p, p'-dihydroxydiciphenyl, 3,3'-dichloro-4,4'-dihydroxydiphenyl, bis ( 4-hydroxyphenyl) sulfone, bis (3,5-
Dihydroxyarylsulfones such as dimethyl-4-hydroxyphenyl) sulfone, resorcinol, hydroquinone, halogen and alkyl substitution such as 1,4-dihydroxy-2,5-dichlorobenzene or 1,4-dihydroxy-3-methylbenzene. Dihydroxybenzenes such as dihydroxybenzene and bis (4-hydroxyphenyl) sulfide, bis (4-
Dihydroxydiphenyl sulfides such as (hydroxyphenyl) sulfoxide and bis (3,5-dibromo-4-hydroxyphenyl) sulfoxide; and sulfoxides. A variety of other dihydric phenols are useful, and are described in U.S. Patent Nos. 2,999,835, 3,028,365 and 3,153,008, all of which are incorporated herein by reference. It has been disclosed. Of course, it is also possible to use two or more different dihydric phenols or a combination of a dihydric phenol and a glycol.

The carbonate precursor can be either a carbonyl halide, a diaryl carbonate or a bishaloformate. The carbonyl halide is
Includes carbonyl bromide, carbonyl chloride and mixtures thereof. The bishaloformate is a bishaloformate of a dihydric phenol such as 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, hydroquinone and the like. Alternatively, it includes a bishaloformate of glycol such as bishaloformate of ethylene glycol. While all of the above carbonate precursors are useful, carbonyl chloride, also known as phosgene, is preferred.

The ester precursor used in the production of the copolyestercarbonate resin of the present invention is a dicarboxylic acid of the general formula HOOC-R ¹ -COOH (V), wherein R ¹ has 6 to 1 carbon atoms.
2). Representative dicarboxylic acids of formula (V) include decandioic acid, undecandioic acid, dodecandioic acid and the like.

A mixture of these dicarboxylic acids may be used. Thus, where the term dicarboxylic acid is used herein, the term is understood to include a mixture of two or more dicarboxylic acids.
Rather than utilizing the dicarboxylic acid itself, it is possible and sometimes preferred to use a reactive derivative of this acid. Illustrative of these reactive derivatives are acid halides. Preferred acid halides are acid dichlorides and acid dibromides. Thus, for example, instead of using dodecane diacid, dodecanoyl dichloride and mixtures thereof can be used. Another reactivity derivation is represented by alkali metal salts of dicarboxylic acids, such as the disodium salt of acid (V).

The branching of the resin results from the incorporation of a polyfunctional organic compound which is a branching agent. The polyfunctional organic compound used in the present invention is 1,1,1-tris- (4-hydroxyphenyl) ethane or a haloformyl derivative thereof. The branching agent is used to make a branched aromatic copolyestercarbonate having an intrinsic viscosity of about 0.3 to 1.0 dl / g measured in methylene chloride at 25 ° C. These branched aromatic copolyester carbonates are substantially free of crosslinking.

In the preparation of the copolyestercarbonate of the present invention, the amount of branching agent to be reacted with the dihydric phenol and the carbonate precursor is such that the amount used is a truly thermoplastic, randomly branched resin; Critical enough that it must be sufficient to produce a resin without cross-linking. If the amount of branching agent used, based on the number of moles of dihydric phenol used, is less than 0.01 mole percent, the resulting polymer will have a non-Newtonian degree of desirability for blow molding and / or melt extrusion purposes. Will not exhibit melt flow properties. Preferably, from 0.01 to about 3.0, based on the total moles of dihydric phenol,
In particular, it is desirable to use 0.01 to 1.0, mol% of a branching agent.

In the most widely practiced polymerization processes, an aqueous solution of an alkali metal salt of a dicarboxylic acid and an aqueous solution of a diphenol in methylene chloride are prepared in the presence of a phase transfer catalyst and a molecular weight regulator, usually a monofunctional phenol. Phosgene is introduced therein. Molecular weight regulators that can be used in the interfacial method include phenol, chroman-I [4- (2,4,4-
Trimethylchromanyl) phenol], pt-butylphenol, 4-p-cumylphenol and the like. Preferably, phenol or pt-butylphenol is used as molecular weight regulator. An effective amount of a molecular weight modifier that gives a modified melt flow value (KI) of 1,000 to 50,000 centiseconds, preferably 5,000 to 30,000 centiseconds, may be used. In general, it is preferred to use 2 to 5 mol%, more preferably 2.5 to 4.5 mol%, of phenol as molecular weight regulator.

The alkali metal salt of a dicarboxylic acid that can be used in the polymerization step can be any of the alkali metal salts selected from the group consisting of alkalis and alkaline earths. Specifically, these are potassium, sodium,
Includes lithium, calcium, magnesium and similar alkali metal salts. The proportions of other reactants used to make the copolyestercarbonate resins of the present invention will vary according to the intended use of the product resin. As described in the U.S. patents mentioned above,
Those skilled in the art are aware of useful ratios. Generally, the amount of ester linkages may be from about 3 to about 90 mole% based on the carbonate linkages. For example, complete reaction of 5 moles of bisphenol A with 4 moles of dodecanoyl dichloride and 1 mole of phosgene will provide a copolyestercarbonate with 80 mole% ester linkages.

A preferred branched copolyestercarbonate for use in the present invention is derived from bisphenol A and phosgene, and has a value of 0.3 as measured at 25 ° C. in methylene chloride.
To 1.0 dl / g. In general, the preferred branched copolyestercarbonates used in the present invention are substantially free of crosslinks. Other embodiments of the present invention include blends of thermoplastic molding compositions containing a small amount (less than 50% by weight) of a polycarbonate homopolymer in a mixture with a branched copolyestercarbonate resin of the present invention.

[0031] Polycarbonate homopolymer resins and their preparation by interfacial polymerization are well known, see, for example, the details described in the following US patents, each of which is incorporated herein by reference: No. 3,028,365, No. 3,334,154, No. 3,275,601, No. 3,915,926, No. 3,030,331, No. 3,169,121, No. 3, Nos. 027,814 and 4,188,314.
Generally, the production method is a method for producing a polyester carbonate as described above, but is a production method carried out in the absence of an ester precursor.

The thermoplastic composition of the present invention may be added to the copolyester carbonate resin of the present invention by adding, for example, an antioxidant,
Antistatic agents, glass, inert fillers such as talc, mica and clay, UV absorbers such as benzophenone, benzotriazole, and the like, all of which are incorporated herein by reference. 489,
Nos. 716, 4,138,379 and 3,83
Hydrolysis stabilizers such as epoxides, impact modifiers, color stabilizers such as organic phosphites, heat stabilizers such as phosphites, release agents and flame retardants disclosed in US Pat. It may be compounded with a conventional molding aid such as an agent. Some particularly useful flame retardants are the alkali and alkaline earth metal salts of sulfonic acids. Flame retardants of this type are disclosed in U.S. Pat. No. 3,9,9, all of which are incorporated herein by reference.
No. 33,734, No. 3,931,100, No. 3,97
No. 8,024, No. 3,948,851, No. 3,92
No. 6,980, No. 3,919,167, No. 3,90
9,490, 3,953,396, 3,95
No. 3,300, No. 3,917,559, No. 3,95
1,910 and 3,940,366.

The following examples describe how and how to make and use the invention, and illustrate the best mode contemplated by the inventor for practicing the invention, but do not limit the scope of the claims. Not to be interpreted. All parts are by weight. The test results are based on the following test methods. Heat deformation temperature under load (DTUL) : Measured according to ASTM-648. Notched Izod Impact Strength (NI) :
Measured on 125 mil thick test specimens according to ASTM D-256. Intrinsic viscosity (IV) : Intrinsic viscosity is measured in methylene chloride at 25 ° C. and is expressed in deciliters / gram (dl / g). Tensile strength and elongation : According to ASTM test method D-638. Flexural yield value and elastic modulus : based on ASTM test method D-790. Melt index ratio (MIR) : ASTM test method D-
Measured at 300 ° C. according to 1238 and expressed in centiseconds. Melt index ratio (MIR) is the ratio of the melt flow rate at two different levels of shear. See the method described in U.S. Pat. No. 4,415,722, column 6, lines 1 to 7, which is incorporated herein by reference. Kasha Index (KI) : A measure of melt viscosity according to the method described in US Pat. No. 4,735,978, which is incorporated herein by reference. The results are expressed in centiseconds or parts measured at 6 minutes and the temperature is 300 ° C. Glass transition temperature (Tg) was determined by differential scanning calorimetry (DS ) using a DuPont 900 thermal analyzer.
Measured by C) and expressed in ° C. Dynatup Impact Strength : Dynatup impact strength measurements were performed on a Dynatup autoloader machine using 125 mil thick 10.16 cm discs. The impact speed of the tap is 148 feet-
12.2 ft / sec giving a pound of impact energy. The average energy for the maximum load of the three measurements was indicated. Specific gravity : Based on ASTM test method D-792. Yellowing index (YI) : ASTM test method D-192
5 under accelerated aging conditions (QUV). The test results are expressed as the exposure time after deterioration by a QUV accelerated weathering tester using a QVA351 lamp. The cycle is 4 hours dark and 8 hours exposure. The change in yellowness is Pacific Scientific Gardner
Laboratory (Pacific Scientific)
Gardner Laboratory) XL-8
It was measured with a 35 type colorimeter. Molecular weight (Mw) : weight average molecular weight (Mw) is 254n
Measured by gel permeation chromatography (GPC) in methylene chloride against a polycarbonate standard using a UV detector of m. Examples 1-3 and Controls 4 and 5: Bisphenol A, 1,1,1-tris- (4-hydro
Dinatriuate of (xyphenyl) ethane and dodecanedioic acid
Copolymerization of dodecane diacid (DDDA) by dissolving dodecanedioic acid free acid (7.2 g, 31 mmol) and NaOH pellets (2.7 g, 68 mmol) in water (180 ml) A salt was produced.

Subsequently, the following procedure was carried out to produce three batches of the resin of the present invention (Examples 1 to 3) in which various proportions of the branching agent were blended. A mechanical stirrer, a pH probe, a tube for introducing a caustic soda aqueous solution (50%), a Claisen adapter equipped with a dry ice condenser, and a gas introducing tube were attached to a 2000 ml five-neck Morton flask with a bottom outlet. In a flask, bisphenol A (BPA) (71 g, 311 mmol) and a predetermined ratio of 1,1,1-tris- (4
-Hydroxyphenyl) ethane, triethylamine (0.9 ml), p-cumylphenol (2.0 g, 9
Mmol), methylene chloride (220 ml) and the above prepared DDDA disodium salt solution. Next, phosgene was introduced at a rate of 2 g / min while maintaining the pH at 8 by adding sodium hydroxide over 10 minutes. Thereafter, the introduction of phosgene was continued for a further 10 minutes while the pH was raised and maintained at approximately 11.
The total amount of phosgene added was 40 g (400 mmol). Subsequently, the pH is adjusted to 11 to 11.5, the organic phase is separated from the brine layer and washed with 2% hydrochloric acid (3.
× 300 ml) and washing with deionized water (5 × 30
0 ml).

The product copolymer was separated from the purified organic solution by steam precipitation. The wet powder thus obtained was dried with a Vertmix dryer. 1,1,1-Tris used
The properties of the (4-hydroxyphenyl) ethane branching agent and the resulting resin are summarized in Table 1 below. The first batch (Example 1) was prepared without a branching agent as a comparative control. Examples 4 and 5 are not examples of the present invention, but are provided as comparative controls.

[0036]

KI Tg example of TABLE 1 diacid THPE ^a IV powder (mol%) (mol%) (dl / g) (at 300 ° C.) (° C.): 1 (control) 9 0 0.58 3050 127 2 9 0.37 0.57 4980 128 3 9 0.36 0.58 4770 127 4 (control) 0 0 0.58 6000 148 5 (control) 0 0.37 0.58 12000 148 ^a: (THPE Mol) / (BPA mol + DDDA mol)
And determined by HPLC analysis of the hydrolysis products.

As shown in Table 1 above, to the polymer chain
The effect of the introduction of aliphatic diacids is that poly
Improves melt flow properties as well as mer formation
You. Examples 6 to 11: General Procedure of Examples 1 to 3 above
According to the formula, 0.36 mol% of 1,1,1-tris- (4
-Hydroxyphenyl) ethane branching agent to give an additional 6
Individual batches of resin were produced. The composition is 50% by weight
Pre-equilibrated with 0.5 gallon of sodium hydroxide solution. 5 minutes
After the pre-equilibration of
Maintained for 41 minutes. Each batch of resin product is listed in Table 2 below.
The characteristics were obtained by testing as described in Table 1. Yellowness of each batch
The index was about 2 to 2.5.

[0038]

TABLE 2 (at 300 ° C.) KI Tg Example IV Mw powder (℃): 6 0.64 363000 7740 129 7 0.65 375000 10690 128 8 0.63 357000 9250 128 9 0.65 344000 6760 127 10 0.61 323000 4870 127 11 0.61 312000 3900 127 Examples 12-14: The resin obtained in Example 11 above was compounded with three different molding formulations (Examples 12-14). .

The first formulation, Example 12, is based on the antioxidant (0.05 phr) manufactured by Ciba-Geigy Corp. under the trade name Irgafos® 168. ) And Emery Chemical
Co. ), A polyalphaolefin release agent (0.5 ml / 1) available under the trade name QUANTUM (registered trademark) 3004 (formerly Emery 3004).
00g). The other two formulations (Examples 13 and 1)
4) further includes Owens-Corning Fiberglass.
s Co. OCF 415CA shear glass fiber, commercially available from Co., Ltd.), at a level of 4.6 and 10% by weight, respectively. The compounding ratio of glass as a filler is
Generally it is 1 to 20% by weight, preferably 1 to 15% by weight of the molding composition.

The three formulations were profile extruded for glazing bead beads. The branched copolyestercarbonate formulation was compared to a branched polycarbonate homopolymer in view of the development of thermoplastic materials used in window seal profiles. As expected, Comparative Example 12 demonstrated extrusion at a lower temperature than the polycarbonate homopolymer, and Comparative Example 12 was also extruded at lower torque,
There was an increase in the central flow in the channel die and the surface smoothness was improved. Higher impact strength was observed.

Various glass-filled formulations were also extrudable at lower temperatures than polycarbonate homopolymers. Testing of the formulations using the copolyestercarbonates of Examples 12 to 14 gave the test results shown in Table 3 below.

[0042]

TABLE 3 Example 12 13 14 Glass content (%) 0 4.6 10.0 at 300 ℃ KI6 ^{(centiseconds) 5410 - - MIR * 2.0 2.4} 2.3 Notched Izod (J / m) 886 (100 %) ^** 112 (0%) ^** 197 (60%) ^** DynaTap (J) 65 41 35 Tensile strength (Yield, MPa) 63 64 65 Tensile strength (break, MPa) 61 48 48 Tensile elongation (%) 80 9 5 Flexural strength (Yield, MPa) 92 98 104 Flexural modulus (MPa) 2262 2788 3476 DTUL at 1.8 MPa (° C) 111 112 113 Specific gravity 1.18 1.22 1.25 ^* : Linear Newton flowable polycarbonate The value of the melt index ratio (MIR) for a homopolymer is typically less than 1.4, and that for a branched polycarbonate homopolymer is typically greater than 1.5.

^** : Values in parentheses indicate the percentage of samples that show ductility at break. Example 15: Except that dodecane diacid used in Example 1 above was replaced by 10 mol% of sebacic acid and that the proportion of THPE used was 0.4 mol%,
The general procedure of Example 1 was repeated.

The product resin was tested to obtain the following properties: IV 0.45 KI6 (centisecond) 1910 KI part 1850 Notched Izod (J / m) 640 (1
00% ductility): Dynatup (J) 50 (1
00% ductility): Tensile strength (yield, MPa) 61 Tensile strength (rupture, MPa) 52 Tensile elongation (%) 0.5 Flexural strength (yield, MPa) 92 Flexural modulus (MPa) 2245 Tg (° C.) ) 132 DTUL at 1.8 MPa (° C.) 113 The desired non-Newtonian flow behavior is evident. Examples 16 to 19: A series of resin batches were produced as follows.

In a stirring compounding tank lined with 150 gallons of glass, DDDA (20 pounds, 39.1 moles), deionized water (40 gallons) and 50% by weight caustic soda (1.2 gallons, 85 gallons). .2 mol).
The slurry was stirred for 20 minutes to ensure complete dissolution of DDDA. Next, to prepare the rest of the batch,
BPA (200 pounds, 398 moles), THPE (1.
1.09 lbs, 1.6 moles or 1.62 lbs.
4 mol), deionized water (20 gallons), methylene chloride (52 gallons), sodium gluconate (0.36 pounds), 90% by weight phenol / water mixture (3.0 pounds) and triethylamine (1120 ml, 800 g)
Or 2 mol% based on BPA). The mixture was stirred and then transferred to the phosgenation reactor. The 20 gallons of methylene chloride used to flush the compounding tank were also transferred to the reactor. 30 compounds
As soon as the 0 gallon glass lined reactor was reached, the introduction of the phosgene stream was started. A phosgene flow rate of 300 pounds / hour was maintained for 23 minutes. Until 65 lbs of phosgene was added, the pH of the reaction was maintained between 8 and 8.5 by adding a 50% by weight aqueous solution of caustic soda. The pH was then raised to 10.5 in 5 minutes and held at that value until 115 pounds of phosgene was added to the reactor. When the integrator reached 115 pounds, the phosgene flow was stopped. Excess phosgene was discharged from the reactor and a sample was taken for residual BPA analysis. The reaction was purified, separated and dried by the steps described in Examples 1-3 above.

The properties observed for the resin produced are shown in Table 4 below.

[0047]

Table 4 Table 4 THPE powder KI Tg Example IV Mw (at 300 ° C.) ^{(mol%) a (℃): 16} 0.60 35000 0.26 9100 128 17 0.58 34000 0.33 6500 127 18 0.58 34000 0.31 6300 127 19 0.61 37800 0.44 10600 129 a: (THPE mol) / (BPA mol + DDDA mol)
And determined by HPLC analysis of the hydrolysis products.

The resins prepared in Examples 17 and 18 were compounded with the quantum release agent (0.5 ml / 100 g) described above and extruded as shown in Examples 12-14 above. The test was performed and the physical properties shown in Table 5 below were observed.

[0049]

Table 5 Example 17 18 at 300 ℃ KI6 (centiseconds) 5700 11,000 Notched Izod (J / m) 694 (100 %) * 534 (60%) * Dynatup (J) 65 57 Tensile strength (yield, MPa) 63 63 Tensile strength (rupture, MPa) 65 49 Tensile elongation (%) 0.6 0.2 Flexural strength (yield, MPa) 89 89 Flexural modulus (MPa) 2157 2162 1 DTUL at 0.8 MPa (° C.) 112 108 The formulations of Examples 17 and 18 exhibited non-Newtonian flow behavior. ^* : Percentage of sample that is ductile at break

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-3-182524 (JP, A) JP-A-3-212424 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 63/64

Claims (10)

(57) [Claims] 1. A compound of the formula (I) Wherein D is a divalent aromatic residue of a dihydric phenol used in the polymerization reaction for production, and a polymer main chain composed of repeating carbonate structural units, and a compound represented by the formula (II): (Wherein, n 4 to an integer of 12) a thermoplastic branched copolyestercarbonates with circular or repeating carboxyl chain units of the above formula (I) and the unit of (II) Formula (III ) Irregularly it has been randomly separated by branch moieties, to 0.3 as measured in methylene chloride at 25 ° C.
Has an intrinsic viscosity of 1.0 dl / g, thermally shows the non-Newtonian flow behavior when plasticized, less than 145 ° C. Gala
A thermoplastic branched copolyestercarbonate having a transition temperature . 2. The copolyestercarbonate according to claim 1, wherein n is 8. 3. The copolyestercarbonate according to claim 1, wherein n is 10. 4. The copolyestercarbonate of claim 1 having an intrinsic viscosity in the range of 0.3 to 1.0 dl / g . 5. A thermoplastic molding composition containing the copolyestercarbonate according to claim 1 and glass fiber in a proportion as a filler. 6. An article molded from the copolyestercarbonate of claim 1. 7. D is a compound of the formula (IV) (In the formula, A 1 to a divalent hydrocarbon radical containing 15 carbon atoms, 1 to substituted divalent hydrocarbon radical containing substituents such as carbon atoms and halogens 15, -S -, - S- S-,
-S (= O)-, -S (= O) _2- , -O- or-
And each X is hydrogen, halogen, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aryl-substituted alkyl group having 7 to 14 carbon atoms. Independently of the group consisting of monovalent hydrocarbon groups such as alkyl-substituted aryl groups having 7 to 14 carbon atoms, alkoxy groups having 1 to 8 carbon atoms or aryloxy groups having 6 to 18 carbon atoms. Wherein m is 0 or 1, and a is an integer of 0 to 5). 8. The copolyestercarbonate of claim 7, wherein A represents propylene, X is hydrogen, m is 1 and a is 1. 9. A compound of the formula (I) (Where D is a divalent aromatic residue of a dihydric phenol used in the polymerization reaction for production) and a polymer main chain composed of repeating carbonate structural units and a compound represented by the formula (II): A thermoplastic branched copolyestercarbonate having cyclic or recurring carboxyl chain units wherein n is an integer from 4 to 12 wherein the above formulas (I) and (II)
Is in the formula From 0.3 to 0.3, measured in methylene chloride at 25 ° C. , randomly and randomly separated by the branches of
Gala having an intrinsic viscosity of 1.0 dl / g and less than 145 ° C.
A thermoplastic branched copolyestercarbonate having a rearrangement temperature and blow moldability . 10. The method according to claim 1, wherein n is an integer of 8 to 10.
2. The copolyestercarbonate according to 1.